The Phenoxyl Radical鈥揥ater Complex鈥擜 Matrix Isolation and Computational Study

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• 作者：Wolfram Sander ; Saonli Roy ; Iakov Polyak ; Juan Manuel Ramirez-Anguita ; Elsa Sanchez-Garcia
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：May 16, 2012
• 年：2012
• 卷：134
• 期：19
• 页码：8222-8230
• 全文大小：445K
• 年卷期：v.134,no.19(May 16, 2012)
• ISSN：1520-5126

文摘

The phenoxyl radical 1 was generated in high yields by flash vacuum pyrolysis of allyl phenyl ether 2 with subsequent trapping of the products in argon at 3 K. In water-doped argon matrices, an OH路路路O complex between 1 and water is formed that could be characterized by IR spectroscopy. Several isotopomers of the complex were generated, and the IR spectra compared to results of density functional theory calculations. Other dimers between 1 and water were not found under these conditions. QM/MM calculations in simulated argon matrices reveal that an OH路路路蟺 complex is unstable even at a time scale of picoseconds. This finding has implications on the related interaction between the tyrosyl radical and the water in biological systems.